JP2015123671A - Laminate and metal-clad laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which has no degradation such as discoloration due to the oxidation of a surface of the laminate even if placed under a high temperature over a long period of time and has excellent insulation strength, a small dielectric constant and excellent transmission characteristics, and a metal-clad laminate.SOLUTION: There is provided a laminate having a thickness of 2 mm or less which is obtained by laminating at least three layers in this order: a layer composed of a crosslinkable resin molded body (A) having resin layers on both surfaces of a fibrous support, a layer composed of a crosslinkable resin molded body (B) having a resin layer containing an inorganic filler and a layer composed of the crosslinkable resin molded body (A). The layer composed of the crosslinkable resin molded body (A) is disposed on both outermost surface layers of the laminate, the thickness (TA) of the layer composed of the crosslinkable resin molded body (A) is smaller than the thickness (TB) of the layer (B) composed of the crosslinkable resin molded body (B) and the ratio (TpB/TB) between the total thickness (TpB) of the resin layer constituting the crosslinkable resin molded body (B) and the thickness (TB) of the layer composed of the crosslinkable resin molded body (B) is 0.4 to 1.0.

Description

  The present invention relates to a laminate and a metal-clad laminate excellent in insulation strength, having a low relative dielectric constant and excellent transmission characteristics even when left at high temperatures for a long time. .

  With recent downsizing and thinning of electronic parts and electronic devices, circuit boards and the like used for these are also required to be downsized and thinned. Therefore, it is necessary to form a higher-density circuit wiring pattern on the circuit board.

  Conventionally, in order to form such a high-density circuit wiring pattern, a multilayer circuit board is used and the thickness of each layer constituting the circuit board is reduced. From the viewpoint of maintaining the mechanical strength of the circuit board even when the circuit board is thinned, a material such as glass fiber is used as a material for forming the interlayer insulating layer of the multilayer circuit board. A method using a prepreg containing a substrate has been studied.

However, when placed at a high temperature for a long time, there is a problem that the surface layer of the prepreg discolors and heat deteriorates.
In order to solve this problem, Patent Document 1 discloses a laminate in which an epoxy resin layer having a thickness of 2 μm is laminated as an antioxidant resin layer. However, in the examples in this document, only an evaluation at a relatively low temperature (125 ° C.) is performed, and a test when placed under a high temperature is not performed.
Patent Document 2 discloses a laminate in which a plurality of fiber base layers in a laminate are arranged at specific positions. However, the laminate described in this document has a high ratio of the thickness of the fiber base material to the thickness of the laminate and the resin content is small, so that the relative dielectric constant may be increased (transmission characteristics may be deteriorated).

Patent Document 3 discloses a laminate in which a first resin layer, a fiber base material, and a second resin layer are laminated in this order, and the second resin layer is thicker than the first resin layer.
However, the laminate described in this document is intended to improve the embedding property, and the reliability when it is placed at a high temperature for a long time is insufficient.

JP 2009-277893 A JP 2012-228879 A JP 2011-068907 A

  The present invention has been made in view of the above-described conventional technology, and even when it is placed at a high temperature for a long time, the surface of the laminate is not deteriorated due to oxidation or discoloration, and the insulation strength is improved. An object of the present invention is to provide a laminate that is excellent and has a low dielectric constant and excellent transmission characteristics.

The resin component in the laminate is generally easily oxidized at a high temperature, and there is a problem that cracks occur when the resin is oxidized. In order to solve this problem, it is conceivable to reduce the amount of resin in the laminated body. However, if this is done, the effect of suppressing oxidation is exhibited, but a new problem arises in that the dielectric constant increases and the transmission characteristics deteriorate.
Accordingly, the present inventors have arranged a prepreg having a large amount of resin and having a fibrous support on the surface thereof in a laminated body composed of a plurality of prepregs (layers of a crosslinkable resin molded body). A thin prepreg having resin layers on both sides of the body was disposed. As a result, the thin prepreg placed on the surface has a thin resin layer, so even if the resin on the surface is oxidized for a long time and the surface resin is oxidized, the progress of the oxidation immediately reaches the fibrous support. As a result, it was found that cracks did not deepen, and the present invention was completed.

Thus, according to the present invention, the laminates (1) to (6) and the metal-clad laminate (7) are provided.
(1) A layer composed of a crosslinkable resin molded body (A) having a resin layer on both surfaces of a fibrous support, a layer composed of a crosslinkable resin molded body (B) having a resin layer containing an inorganic filler, and In the order of the layer made of the crosslinkable resin molded body (A), at least 3 layers are laminated, and the laminate has a thickness of 2 mm or less,
The layer composed of the crosslinkable resin molded body (A) is disposed on both outermost layers of the laminate,
The thickness (TA) of the layer composed of the crosslinkable resin molded body (A) is smaller than the thickness (TB) of the layer (B) composed of the crosslinkable resin molded body (B), and
The ratio (TpB / TB) of the total thickness (TpB) of the resin layer constituting the crosslinkable resin molded body (B) and the thickness (TB) of the layer made of the crosslinkable resin molded body (B) is 0.4 or more. A laminate having a thickness of 1.0 or less.

(2) The resin layer in the layer (A) of the crosslinkable resin molded body and the resin layer in the layer (B) of the crosslinkable resin molded body are layers containing a cycloolefin resin. (1) The laminated body as described in.
(3) The ratio (TpA / TA) between the total thickness (TpA) of the resin layers constituting the crosslinkable resin molded body (A) and the thickness (TA) of the layer made of the crosslinkable resin molded body (A). The laminate according to (1) or (2), which is 0.3 or more and less than 1.0.
(4) The laminate according to any one of (1) to (3), wherein the fibrous support has a thickness of 10 to 50 μm.

(5) The laminate according to any one of (1) to (4), wherein a relative dielectric constant calculated from a dielectric constant measured at a temperature of 20 ° C. and a frequency of 1 GHz using an impedance analyzer is 3.5 or less. body.
(6) The crosslinkable resin molded product (A) obtained by polymerizing the polymerizable composition after applying or impregnating a polymerizable support containing a metathesis polymerizable monomer to a fibrous support. The laminate according to any one of (1) to (5).
(7) A metal-clad laminate in which a metal foil is laminated on at least one surface of the laminate according to (1) to (6).

According to the present invention, even when it is placed at a high temperature for a long time, there is no deterioration such as the surface being oxidized and discoloring, excellent insulation strength, low dielectric constant, and excellent transmission characteristics. Body and metal-clad laminates are provided.
The laminate and metal-clad laminate of the present invention can be suitably used for printed wiring boards.

It is a figure which shows sectional drawing of the layer which consists of a crosslinkable resin molding (A), and the centerline of a fibrous support body. It is sectional drawing which shows the lamination | stacking state of an example of the laminated body of this invention.

Hereinafter, the present invention will be described in detail by dividing it into 1) a laminate and 2) a metal-clad laminate.
1) Laminate The laminate of the present invention comprises a crosslinkable resin molded body (B) having a layer composed of a crosslinkable resin molded body (A) having resin layers on both sides of a fibrous support and a resin layer containing an inorganic filler. ) And a layer made of the crosslinkable resin molded body (A) in this order, and a laminate having a thickness of 2 mm or less, wherein the crosslinkable resin molded body ( The layer made of A) is arranged on both outermost layers of the laminate, and the thickness (TA) of the layer made of the crosslinkable resin molded body (A) is the thickness of the layer made of the crosslinkable resin molded body (B) ( TB) and the ratio (TpB /) of the total thickness (TpB) of the resin layer constituting the crosslinkable resin molded body (B) and the thickness (TB) of the layer made of the crosslinkable resin molded body (B). TB) is 0.4 or more and 1.0 or less.

(1) Layer composed of crosslinkable resin molded body (A) The laminate of the present invention has “resin layers (hereinafter referred to as“ fiber layers ”on both sides of the fibrous support”) on its outermost layer (layers located on both surfaces of the laminate). A layer made of a crosslinkable resin molded body (A) having a “resin layer (a)” (hereinafter also referred to as “crosslinkable resin molded body (A) layer”).

<Fibrous support>
The fibrous support is a sheet-like product made of a fibrous material located at the center of the crosslinkable resin molded body (A) layer.
As the fiber constituting the fibrous support to be used, inorganic and / or organic fibers can be used. For example, PET (polyethylene terephthalate) fiber, aramid fiber, ultrahigh molecular polyethylene fiber, polyamide (nylon) fiber, and Organic fibers such as liquid crystal polyester fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, butene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers; It is done. Among these, glass fiber is preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used. These can be used alone or in combination of two or more.

  As the fibrous support composed of glass fibers, those known as glass cloths for printed wiring boards can be used. As the weave structure of glass cloth, plain weave, Nanako weave, twill weave, satin weave, imitation weave, leash weave and the like are preferable.

  The thickness of the fibrous support is usually 5 to 150 μm, preferably 10 to 100 μm, more preferably 10 to 50 μm.

The fibrous support is preferably subjected to a fiber opening treatment from the viewpoint of suppressing in-plane variation in dielectric constant. The degree of opening is not particularly limited, but is usually 10 cm ³ / cm ² / s or less, preferably 5 cm ³ / cm ² / s or less, in terms of the air permeability defined in JIS standard R 3420.

<Resin layer (a)>
As the resin used for the resin layer (a), a conventionally known thermosetting resin used for prepreg production can be used. Examples of the thermosetting resin include epoxy resins, polyimide resins, phenol resins, melamine resins, bismaleimide triazine resins, and cycloolefin resins.
Among these, a cycloolefin resin is preferable from the viewpoint of obtaining an excellent effect as a circuit board.

The resin layer (a) can be formed by impregnating the fibrous support with the above-described thermosetting resin solution (coating solution) and drying and removing the solvent.
The resin layer (a) made of cycloolefin resin can also be obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent and the like. According to this method, a resin layer made of cycloolefin resin can be easily and efficiently produced.

<Polymerizable composition>
(I) Cycloolefin monomer The cycloolefin monomer is a compound having an alicyclic structure composed of carbon atoms and having at least one polymerizable carbon-carbon double bond in the alicyclic structure. .

  In the present specification, the “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of ring-opening polymerization. There are various types of ring-opening polymerization such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, metathesis polymerization is preferable.

Examples of the alicyclic structure possessed by the cycloolefin monomer include monocyclic, polycyclic, condensed polycyclic, bridged ring, and combination polycyclic thereof. Although there is no limitation in particular in carbon number which comprises each alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. Among these, a polycyclic structure is preferable from the viewpoint of highly balancing the dielectric properties and heat resistance of the obtained laminate.
As the cycloolefin monomer having a polycyclic structure, a norbornene-based monomer is particularly preferable. Here, the “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. For example, norbornenes, dicyclopentadiene, tetracyclododecenes and the like can be mentioned.

The cycloolefin monomer may have a substituent at any position. Examples of the substituent include hydrocarbon groups having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group; polar groups such as a carboxyl group and an acid anhydride group;
A cycloolefin monomer can be used individually by 1 type or in combination of 2 or more types.

  Among these, in the present invention, as the cycloolefin monomer, the cycloolefin monomer (a) having an alicyclic structure in the molecule and having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure. And having in the molecule at least one group selected from an alkenyl group having 2 to 6 carbon atoms, an alkylidene group having 1 to 6 carbon atoms, and a vinylidene group, and an alicyclic structure, And a cycloolefin monomer (b) having a carbon-carbon double bond (excluding the cycloolefin monomer (a)) or a cycloolefin monomer (b).

When the cycloolefin monomer (a) and the cycloolefin monomer (b) are mixed and used, the content ratio of the cycloolefin monomer (a) in the monomer mixture is 5 to 5 in all monomers constituting the monomer mixture. It is preferably 99.9% by mass, more preferably 20 to 95% by mass, still more preferably 40 to 90% by mass, and particularly preferably 50 to 80% by mass. The content ratio of the cycloolefin monomer (b) in the monomer mixture is preferably 0.1 to 95% by mass and more preferably 5 to 80% by mass in the total monomer constituting the monomer mixture. Preferably, it is 10-60 mass%, More preferably, it is 20-50 mass%.
If the content of the cycloolefin monomer (a) is too small, the peel strength of the resulting laminate may be reduced. On the other hand, if the content is too high, the heat resistance of the resulting laminate may be reduced.

  In the cycloolefin monomer (a), the “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction. In particular, it refers to a radical crosslinking reaction. Crosslinkable carbon-carbon unsaturated bonds include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or aliphatic carbon-carbon triple bonds. In the present invention, it usually means an aliphatic carbon-carbon double bond. And the cycloolefin monomer (b) used by this invention consists of what all carbon atoms which comprise such a crosslinkable carbon-carbon unsaturated bond comprise a part of alicyclic structure. .

  As such a cycloolefin monomer (a), a monocyclic cycloolefin monomer having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure, and a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure. Examples include norbornene-based monomers, and norbornene-based monomers having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure are preferable.

  Specific examples of the cycloolefin monomer (a) include dicyclopentadiene, methyl-dicyclopentadiene, dimethyldicyclopentadiene, ethyldicyclopentadiene, 2,5-norbornadiene, 5-methyl-2,5-norbornadiene, 5- Examples thereof include compounds having two carbon-carbon unsaturated bonds in the alicyclic structure such as phenyl-2,5-norbornadiene and 5,6-dimethyl-2,5-norbornadiene. These can be used alone or in combination of two or more. Among these, dicyclopentadiene is preferable from the viewpoint that the effects of the present invention become more remarkable.

  The cycloolefin monomer (b) has at least one group selected from an alkenyl group having 2 to 6 carbon atoms, an alkylidene group having 1 to 6 carbon atoms, and a vinylidene group in the molecule, and an alicyclic structure. And it is an alicyclic olefin monomer which has a carbon-carbon double bond in an alicyclic structure. However, the cycloolefin monomer (a) is excluded.

As said C2-C6 alkenyl group, a vinyl group, 1-propenyl group, an allyl group, a butenyl group etc. are mentioned, A vinyl group and 1-propenyl group are preferable.
Examples of the alkylidene group having 1 to 6 carbon atoms include a methylidene group, an ethylidene group, a propylidene group, and a butylidene group.
As for the alicyclic structure which a cycloolefin monomer (b) has, the thing similar to the alicyclic structure which the said cycloolefin monomer (a) has is mentioned.

Specific examples of the cycloolefin monomer (b) include 9-methylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-n-propylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-Isopropylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-Vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-isopropenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-allyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9- (1-propenyl) tetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-4-ene;
5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5,6-diethylidene-2-norbornene, n-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene And norbornenes such as 5-isopropenyl-2-norbornene, 5- (1-propenyl) -2-norbornene, 5-allyl-2-norbornene; and the like.

These can be used alone or in combination of two or more.
Among these, tetracyclododecenes are preferable from the viewpoint that the effects of the present invention become more prominent, and 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (ETD) is particularly preferred.

  In addition to the cycloolefin monomer (a) and the cycloolefin monomer (b), the polymerizable composition may contain another cycloolefin monomer (c).

  Examples of other cycloolefin monomers (c) include norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, and 1-methyl. 2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8- Jime -1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3- Dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahi Lonaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloro- 2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro-2-norbornene, 5,5,6-trifluoro-6-trifluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, Examples include 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, and 5-cyano-2-norbornene. These can be used alone or in combination of two or more.

  In the case of using the cycloolefin monomer (c), the content ratio of the cycloolefin monomer (c) is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less in all monomers. .

(Ii) Metathesis polymerization catalyst The polymerizable composition preferably contains a metathesis polymerization catalyst for metathesis ring-opening (co) polymerization of the above-described cycloolefin monomer.
As the metathesis polymerization catalyst to be used, a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom is usually mentioned. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium. Among these, a group 8 ruthenium or osmium complex is preferably used as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. The ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, so it is excellent in productivity of the crosslinkable resin molded product, and the resulting crosslinkable resin molded product has less odor derived from unreacted monomers and is excellent in workability. . The ruthenium carbene complex is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used for production in the atmosphere.

  Examples of the ruthenium carbene complex include those represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), R ¹¹ and R ¹² may each independently contain a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. A good C1-C20 hydrocarbon group is represented.

X ¹¹ and X ¹² each independently represent an arbitrary anionic ligand. An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound. A heteroatom means an atom of Groups 15 and 16 of the Periodic Table, and specific examples include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, and S atoms are preferable, and N atom is particularly preferable.

  The neutral electron donating compound may be any ligand as long as it has a neutral charge when pulled away from the central metal. Specific examples thereof include phosphines, ethers and pyridines, phosphines are preferable, and trialkylphosphine is more preferable.

In the general formulas (i) and (ii), R ¹¹ and R ¹² may be bonded to each other to form a ring, and further R ¹¹ , R ¹² , X ¹¹ , X ¹² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

In the present invention, a compound having a heterocyclic structure is preferred as the heteroatom-containing carbene compound from the viewpoint of increasing production efficiency of a crosslinkable resin molded article and the like. As a hetero atom which comprises a heterocyclic structure, an O atom, an N atom, etc. are mentioned, for example, Preferably it is an N atom. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.
Examples of the compound having a heterocyclic structure include compounds represented by the following general formula (iii) or general formula (iv).

In the formula, R ^{13 to} R ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R ^{13 to} R ¹⁶ may be bonded to each other in any combination to form a ring.
Specific examples of the compound having a heterocyclic structure include 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diidene. (1-phenylethyl) -4-imidazoline-2-ylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1,3-dimesitylimidazolidin-2-ylidene, 1,3- Examples include dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

The ruthenium carbene complex having such a compound having a heterocyclic structure as a ligand is represented by the above general formula (i) or (ii), and is composed of a compound having a heterocyclic structure as L ¹ or L ^2. Examples thereof include a ruthenium carbene complex having a ligand.

  Specific examples of the ruthenium carbene complex having a ligand composed of a compound having a heterocyclic structure include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydro Imidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole -5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) Examples thereof include a ruthenium carbene complex in which a compound having a heterocyclic structure as a ligand such as pyridine ruthenium dichloride and a neutral electron donating compound other than the compound are bonded.

  These metathesis polymerization catalysts are used alone or in combination of two or more. The use amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: in a molar ratio of (metal atoms in the catalyst: total monomers). The range is 1,000,000, more preferably 1: 10,000 to 1: 500,000.

  If desired, the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

(Iii) Crosslinking agent The polymerizable composition preferably contains a crosslinking agent for the purpose of inducing a crosslinking reaction in the crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition.
The resulting crosslinkable resin molded article can be a postcrosslinkable thermoplastic resin. Here, “after-crosslinking is possible” means that the resin can be heated to advance a crosslinking reaction to form a crosslinked resin.

  As the crosslinking agent, a radical generator is preferably used. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, with organic peroxides being preferred.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methylcycl Peroxyketals such as rhohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl-3, And cyclic peroxides such as 6,9-trimethyl-1,4,7-triperoxonane and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane. Among these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferable in that there are few obstacles to the polymerization reaction.

  Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone, 2,6-bis (4'-azidobenzal) cyclohexanone, and the like.

  Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.

  When a radical generator is used as the crosslinking agent, the 1 minute half-life temperature of the radical generator is appropriately selected depending on the crosslinking conditions, but is usually 100 to 300 ° C, preferably 150 to 250 ° C, more preferably. It is the range of 160-230 degreeC. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, NOF Corporation).

  A crosslinking agent can be used individually or in combination of 2 types or more, respectively. As content of the crosslinking agent in the polymeric composition used for this invention, it is 0.01-10 weight part normally with respect to 100 weight part of all the monomers, Preferably it is 0.1-10 weight part, More Preferably it is the range of 0.5-5 weight part.

(Iv) Chain transfer agent The polymerizable composition preferably further contains a chain transfer agent. When a chain transfer agent is blended in the polymerizable composition, the followability at the time of heating and melting can be further improved on the surface of the crosslinkable resin molded body obtained by bulk polymerization of the composition. Therefore, in a laminate obtained by laminating a crosslinkable resin molded article obtained by using a polymerizable composition containing a chain transfer agent, heating and melting, and crosslinking, the interlayer adhesion is further improved. This is preferable because the peel strength is further improved. The chain transfer agent may further have one or more crosslinkable carbon-carbon unsaturated bonds. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a vinyl group or a vinylidene group.

  Specific examples of the chain transfer agent include hydrocarbon compounds having no hetero atom such as 1-hexene, 2-hexene, styrene, vinylcyclohexane, divinylbenzene; allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl. Ketone, 2- (diethylamino) ethyl acrylate, 4-vinylaniline, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol diacrylate, allyltrivinylsilane, tetraallylsilane Hydrocarbon compounds having a heteroatom such as; These can be used alone or in combination of two or more. Among these, a hydrocarbon compound having no hetero atom is preferable, and styrene and divinylbenzene are more preferable from the viewpoint that the obtained laminate can be excellent in peel strength and crack resistance.

  As a compounding quantity of a chain transfer agent, Preferably it is 0.2-10 mol with respect to 1 mol of cycloolefin monomers, More preferably, it is 0.5-6 mol. When the blending ratio of the chain transfer agent is too small, the laminate property of the resulting crosslinkable resin molded product tends to be lowered. On the other hand, when it is too much, the peel strength of the obtained laminate tends to be lowered.

(V) Other additives The polymerizable composition may contain, as desired, other additives in addition to the above components, such as a filler, a flame retardant, a polymerization regulator, a polymerization reaction retarder, an antioxidant, a crosslinking aid, It may further contain other compounding agents.
Any of these components can be used alone or in combination of two or more. The addition amount may be appropriately selected within a range that does not impair the effects of the present invention.

  The filler is not particularly limited as long as it is generally used industrially, and both inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. By mix | blending a filler with the polymeric composition of this invention, the improvement of the mechanical strength and heat resistance of the crosslinked resin molding and laminated body which are obtained becomes possible.

As inorganic fillers, metal hydroxide fillers such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide; silica balloon, alumina, iron oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite, magnesium oxide, Metal oxide fillers such as titanium dioxide, zinc oxide and silicon dioxide (silica); Metal chloride fillers such as sodium chloride and calcium chloride; Metal sulfate fillers such as sodium sulfate and sodium hydrogen sulfate; Nitric acid Metal nitrate fillers such as sodium and calcium nitrate; Metal phosphate fillers such as sodium hydrogen phosphate and sodium dihydrogen phosphate; Metal titanates such as calcium titanate, strontium titanate and barium titanate Filler; sodium carbonate, calcium carbonate, magnesium carbonate Metal carbonate fillers such as sodium hydrogen carbonate; Carbide fillers such as boron carbide and silicon carbide; Nitride fillers such as boron nitride, aluminum nitride and silicon nitride; Aluminum, nickel, magnesium, copper, zinc Metal particle fillers such as iron, gold, silver, lead, tungsten; silicate fillers such as talc, clay, montmorillonite, calcium silicate, glass, glass balloon mica, kaolin, fly ash; glass powder; And carbon particles such as carbon black, graphite, activated carbon, and carbon balloon.
Examples of the organic filler include compound particles such as wood flour, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics.
The blending amount of the filler is usually 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of all monomers.

As the flame retardant, any industrially used flame retardant can be used without any particular limitation. For example, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, chlorinated polystyrene, chlorinated polyethylene, highly chlorinated polypropylene, chlorosulfonated polyethylene, hexabromobenzene, decabromodiphenyl oxide Bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-hydroxy-3,5-dibromophenylpropane) ), Halogenated flame retardants such as pentabromotoluene; metal hydroxide flame retardants such as magnesium hydroxide and aluminum hydroxide; phosphorus-containing flame retardants; nitrogen-containing flame retardants; non-halogens such as antimony compounds such as antimony trioxide Emissions-based flame retardant; and the like.
The blending amount of the flame retardant is usually in the range of 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the total monomers.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of the polymerization regulator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like. These polymerization regulators can be used alone or in combination of two or more. In the case of using a polymerization regulator, the blending amount of the polymerization regulator is a molar ratio (metal atom in the metathesis polymerization catalyst: polymerization regulator), preferably 1: 0.05 to 1: 100, more preferably 1: It is in the range of 0.2 to 1:20, more preferably 1: 0.5 to 1:10.

  The polymerization reaction retarder is used for the purpose of suppressing an increase in viscosity of the polymerizable composition used in the present invention and more uniformly impregnating the reinforcing fiber of the composition. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine And the like.

  Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. By blending these antioxidants, a crosslinking reaction It is preferable because the heat resistance of the obtained crosslinked resin molded product and laminate can be improved to a high degree without hindering. Among these, a phenolic antioxidant and an amine antioxidant are preferable, and a phenolic antioxidant is more preferable.

In the present invention, when a radical generator is used as the crosslinking agent, it is preferable to use a crosslinking aid in combination in order to promote the crosslinking reaction. Examples of the crosslinking aid include dioxime compounds such as p-quinonedioxime; methacrylate compounds such as lauryl methacrylate and trimethylolpropane trimethacrylate; fumaric acid compounds such as diallyl fumarate: phthalic acid compounds such as diallyl phthalate; And cyanuric acid compounds such as allyl cyanurate; imide compounds such as maleimide; and the like.
Although the usage-amount of a crosslinking adjuvant is not restrict | limited in particular, It is 0-100 mass parts normally with respect to 100 mass parts of all monomers, Preferably it is 0-50 mass parts.

  As other compounding agents, colorants, light stabilizers, foaming agents and the like can be used. As the colorant, a dye or a pigment is used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  The polymerizable composition can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and separately, an essential component such as a norbornene monomer and a crosslinking agent, In addition, it can be prepared by preparing a liquid (monomer liquid) containing other compounding agents and the like, if desired, adding a catalyst liquid to the monomer liquid, and stirring.

<Crosslinkable resin molded product (A) layer>
A crosslinkable resin molding (A) layer is a layer which has a resin layer (a) on both surfaces of a fibrous support body.
The crosslinkable resin molded body (A) layer is, for example, a method in which the polymerizable composition is applied to and impregnated on both surfaces of the fibrous support, and then the application surface is pressed with a roller or the like, and then bulk polymerization is performed. Alternatively, the polymerizable composition is cast (applied) on a sheet-like support, the fibrous support is overlaid thereon, the polymerizable composition is further applied thereon, and then the application surface is pressed, Can be obtained by a bulk polymerization method.
Among these, the former method in which the polymerizable composition is applied and impregnated and then bulk polymerization is preferable.
When pressing, a protective film may be sandwiched between the roller and the coating surface.

  Examples of the sheet-like support include resin films made of polytetrafluoroethylene, polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, nylon, and the like; iron, stainless steel, copper, aluminum, nickel, chromium, gold And metal foil made of a metal material such as silver.

  Examples of the protective film include the resin film exemplified as the sheet-like support. These surfaces may be subjected to a peeling treatment.

  A method for applying (casting) the polymerizable composition is not particularly limited, and a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, and the like can be used.

  After the fibrous composition is impregnated with the polymerizable composition, it is dried if desired, and then bulk polymerized. Bulk polymerization is usually performed by heating the polymerizable composition to a predetermined temperature. The method for heating the polymerizable composition is not particularly limited, a method of heating on a heating plate, a method of heating while applying pressure using a press (hot pressing), a method of pressing with a heated roller, a heating furnace The method of heating inside is mentioned.

  The temperature for bulk polymerization of the polymerizable composition is usually 30 to 250 ° C., preferably 50 to 200 ° C., more preferably 90 to 150 ° C., and the crosslinking agent, usually a one minute half-life of the radical generator. The temperature is preferably 10 ° C. or less, more preferably 1 minute half-life temperature of 20 ° C. or less. The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes. By heating the polymerizable composition under such conditions, a layer (A) of the crosslinkable resin molded body with less unreacted monomer can be obtained.

  The polymer constituting the crosslinkable resin molded article (A) obtained by bulk polymerization of the polymerizable composition as described above has substantially no crosslink structure and is soluble in, for example, toluene. The molecular weight of the polymer is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably 5,000 to It is in the range of 500,000, more preferably 10,000 to 100,000.

  Although the polymer which comprises the crosslinkable resin molding (A) obtained is a resin molding which can be post-crosslinked, a part of the constituent resin may be crosslinked.

  The polymer constituting the crosslinkable resin molded product (A) is obtained by completing bulk polymerization, and there is no possibility that the polymerization reaction further proceeds during storage. In addition, the crosslinkable resin molded article (A) contains a crosslinking agent, but unless it is heated to a temperature higher than that causing a crosslinking reaction, it does not cause a problem such as a change in surface hardness and is excellent in storage stability.

The resulting crosslinkable resin molded body (A) layer has the layer structure shown in FIG. 1, that is, the resin layer (a) on both sides of the fibrous support. In FIG. 1, a1 and a2 are resin layers, and s is a fibrous support layer.
The thickness (TA) of the crosslinkable resin molded body (A) layer only needs to be smaller than the thickness (TB) of the layer made of the crosslinkable resin molded body (B) described later. Although it depends on the thickness of the layer composed of the crosslinkable resin molded product (B), it is usually 15 to 200 μm, preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The total thickness of the resin layer (a) (TpA, in FIG. 1, the sum of the thickness of the resin layer a1 and the thickness of the resin layer a2) is preferably 5 to 50 μm, more preferably 5 to 30 μm. If it is less than this range, it is difficult to control the thickness, and if it exceeds this range, the effect of the present invention is difficult to obtain.

  Furthermore, the ratio (TpA / TA) between the thickness (TpA) of the resin layer (a) and the thickness (TA) of the crosslinkable resin molded product (A) layer is usually 0.3 or more and less than 1.0, It is preferably 0.5 or more, and more preferably 0.8 or more.

  The larger the value of TpA / TA, the more effectively the occurrence of skew can be prevented. Skew is generated in the following cases. If there is a space (basket hole) in which no warp or weft exists in the layer, the dielectric constant is locally lowered, and variation in the dielectric constant occurs in the order of microns. Since the dielectric constant affects the transmission speed, the transmission speed varies depending on the location. In high-speed transmission, from the viewpoint of reducing noise, a transmission form called a differential system is usually adopted. In this system, signals are sent with a pair of two lines, but if the transmission rates of the two lines are different, the signal waveforms do not match at the exit. The occurrence of such a problem is called skew.

In the crosslinkable resin molded body (A) layer used in the present invention, the center line C (see FIG. 1) of the fibrous support layer is relative to the thickness (TA) of the crosslinkable resin molded body (A) layer. The cross-linkable resin molded body (A) layer is preferably located at a position of 0.2 to 0.8, more preferably at a position of 0.3 to 0.7, and 0.4 to 0.00. 6 is more preferable, and a position of 0.45 to 0.55 is particularly preferable (in the crosslinkable resin molded product (A) layer in FIG. 1, C is 0.5). .
The center line of the fibrous support refers to the midpoint between the highest point and the lowest point of the cross section of the prepreg observed with an SEM photograph.

The dielectric constant of the crosslinkable resin molded product (A) is preferably 4.0 or less, and more preferably 3.5 or less. Further, the dielectric loss tangent of the crosslinkable resin molded body (A) is preferably 0.01 or less, and more preferably 0.005 or less.
The resin layer preferably has a small dielectric constant and dielectric loss tangent.
By reducing the dielectric constant and the dielectric loss tangent, loss during signal transmission can be suppressed. Especially for substrates used in high-frequency bands and substrates with long wiring lengths, the effect of loss is large. By using a substrate material with a low dielectric constant and dielectric loss tangent, it is possible to transmit signals efficiently far away without increasing the output. This can greatly contribute to energy saving during transmission.

(2) Layer Consisting of Crosslinkable Resin Molded Body (B) The laminate of the present invention has a thickness of at least one crosslinkable resin molded body (A) layer other than the crosslinkable resin molded body (A) layer. A layer made of a crosslinkable resin molded body (B) having a large “resin layer containing an inorganic filler (hereinafter sometimes referred to as“ resin layer (b) ”) (hereinafter, crosslinkable resin molded body (B) ) Layer ”).

  As the resin used for the resin layer (b), a conventionally known thermosetting resin used for prepreg production can be used. Specific examples include those listed as resins constituting the resin layer (a). Especially, it is preferable that it is a cycloolefin resin from a viewpoint from which the effect of this invention is acquired more notably.

As an inorganic filler, the thing similar to the inorganic filler illustrated as another additive of the polymerizable composition by the term of the said crosslinkable resin molding (A) layer is mentioned.
Among these, a metal oxide filler is preferable and silicon dioxide (silica) is more preferable because a laminate having a high elastic modulus is easily obtained.
An inorganic filler can be used individually by 1 type or in combination of 2 or more types.
Further, the inorganic filler may be a surface treated with a known silane coupling agent, titanate coupling agent, aluminum coupling agent or the like.

The resin layer (b) can be obtained by a method similar to the method listed as the method for forming the resin layer (a) described above.
The resin layer (b) made of cycloolefin resin can be obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, an inorganic filler, a crosslinking agent, and the like.
The compounding amount of the inorganic filler is usually in the range of 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the total monomers forming the resin layer (b).

The crosslinkable resin molded body (B) layer may or may not contain a fibrous support, but from the viewpoint of reducing skew, it is preferable not to contain it.
When the crosslinkable resin molded body (B) layer contains a fibrous support, it can be produced by the same method as the crosslinkable resin molded body (A) layer.

When the crosslinkable resin molded body (B) layer does not contain a fibrous support, the polymerizable composition for forming the resin layer (b) is cast (applied) on the sheet-like support. Then, after a sheet-like support is bonded to the coated surface, it can be produced by polymerizing bulk polymerization. The method of coating (casting) the polymerizable composition on the sheet-like support, the method of bulk polymerization, the heating temperature, etc. are the same as the method of forming the crosslinkable resin molded product (A) layer.
The crosslinkable resin molded body (B) layer is peeled off and laminated from the sheet-like support.

  The ratio (TpB / TB) between the thickness (TpB) of the resin layer (b) of the crosslinkable resin molded body (B) and the thickness (TB) of the crosslinkable resin molded body (B) layer is 0.4 or more and 1 0.0 or less, preferably 0.5 or more, more preferably 0.8 or more. The larger the value, the smaller the skew. When the crosslinkable resin molded body (B) layer does not contain a fibrous support, TpB / TB is 1.

  The thickness of the crosslinkable resin molded body (B) may be larger than the thickness of the crosslinkable resin molded body (A). Although it depends on the thickness of the crosslinkable resin molded product (A), it is usually 30 to 300 μm, preferably 50 to 200 μm, more preferably 50 to 100 μm.

The dielectric constant of the crosslinkable resin molded product (B) is preferably 4.0 or less, more preferably 3.5 or less, and the dielectric loss tangent of the crosslinkable resin molded product (B) is preferably 0.01 or less. More preferably, it is 0.005 or less.
the reason

(3) Laminate The laminate of the present invention comprises at least three layers of a crosslinkable resin molded body (A) layer, a crosslinkable resin molded body (B) layer, and a crosslinkable resin molded body (A) layer. It is laminated | stacked in order and a crosslinkable resin molded object (A) layer is arrange | positioned at both outermost layers of a laminated body.
That is, the crosslinkable resin molded body (A) layer-crosslinked resin molded body (B) layer-crosslinked resin molded body (A) layer are laminated in this order, and the crosslinked resin molded body (A) layer and the crosslinked resin molded body (B Further layers ((C) layer) may exist between the layers.

  The layer (C) is not particularly limited to a resin material or the like as long as the layer does not hinder the effects of the present invention. Further, it may or may not contain a fibrous support, but preferably has a small dielectric constant and dielectric loss tangent. Furthermore, the (C) layer may be the same as the crosslinkable resin molded body (A) layer or the crosslinkable resin molded body (B) layer.

Specific examples of the layer configuration include the following. However, the laminate of the present invention is not limited to one having the following layer structure.
In the following, the crosslinkable resin molded product (A) layer is abbreviated as (A) layer, and the crosslinkable resin molded product (B) layer is abbreviated as (B) layer.
(I) (A) layer / (B) layer / (A) layer (ii) (A) layer / (B) layer / (C) layer / (A) layer (iii) (A) layer / (B) Layer / (C) layer / (C) layer / (A) layer (iv) (A) layer / (C) layer / (B) layer / (C) layer / (A) layer (v) (A) layer / (C) layer / (B) layer / (C) layer / (C) layer / (A) layer (vi) (A) layer / (C) layer / (C) layer / (B) layer / (C ) Layer / (C) layer / (A) layer

The thickness of the laminate of the present invention is 2 mm or less, preferably 1 mm or less, more preferably 0.4 mm or less.
the reason

  The production method of the laminate is not particularly limited, but usually, the crosslinkable resin molded body (A), the crosslinkable resin molded body (B), and optionally the molded body constituting the (C) layer are laminated in a preferred order. And a method of hot pressing.

The heating temperature at the time of hot pressing is usually 100 to 300 ° C, preferably 150 to 280 ° C, more preferably 180 to 250 ° C.
The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 2 to 10 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).

  A cross-sectional view of an example of the laminate of the present invention is shown in FIG. In FIG. 2, (A1) and (A2) indicate a crosslinkable resin molded body (A) layer, (B) indicates a crosslinkable resin molded body (B) layer, and L indicates (A) layer / (B). The laminated body which consists of a layer / (A) layer is shown.

  In the laminated body of this invention, since the thin crosslinkable resin molding (A) layer is arrange | positioned in the outermost layer, the distance from the surface to a fibrous support body is short. Therefore, even if the resin layer on the surface is oxidized for a long time under high temperature, the oxidation reaction stops when it reaches the fibrous support of the crosslinkable resin molded product (A) layer, so that cracks are not generated. It will never be deep. For this reason, the laminate of the present invention has no deterioration such as discoloration due to oxidation of the surface even when it is placed at a high temperature for a long time, has excellent insulation strength, has a low dielectric constant, and is transmitted. Excellent characteristics.

  The laminated body of the present invention has such characteristics. For example, after the laminated body of the present invention is placed at a high temperature of 200 ° C. for 400 hours, it is oxidized from both surfaces by cross-sectional observation using an optical microscope. The depth (thickness of the discolored portion) is measured, and the degree of oxidation erosion is calculated from the following formula.

  This value is usually 0.4 or less, preferably 0.38 or less in the laminate of the present invention.

Moreover, the laminated body of this invention is excellent in insulation strength. It can be confirmed that the insulation strength is excellent by, for example, placing it at a high temperature of 200 ° C. for 400 hours and measuring the dielectric breakdown voltage holding ratio before and after that.
The laminate of the present invention has a retention rate of usually 0.7 or more, preferably 0.8 or more. The measurement of the dielectric breakdown voltage retention rate can be performed by the method shown in the examples.

  When the laminate of the present invention is heated to a temperature at which the included crosslinking agent is active or higher, the crosslinkable resin molded product undergoes a crosslinking reaction to obtain a laminate of the crosslinked resin molded product.

2) Metal-clad laminate The metal-clad laminate of the present invention is obtained by laminating a metal foil on at least one surface of the laminate of the present invention.
The metal-clad laminate of the present invention comprises (α) a method of laminating a metal foil on one or both sides of the laminate of the present invention, placing this between stainless steel plates, and heating and pressing; When the laminate is manufactured, the crosslinkable resin molded body (A) layer, the crosslinkable resin molded body (B) layer, and the like are laminated in a predetermined order, and the metal foil laminated on the upper and lower sides thereof is hot-pressed. Method.
The hot pressing can be performed by the same method as that for manufacturing the laminate.

  Since the metal foil laminate of the present invention uses the laminate of the present invention, even when it is placed at a high temperature for a long time, the surface does not deteriorate, it has excellent insulation strength, and the ratio Low dielectric constant and excellent transmission characteristics.

  The metal-clad laminate of the present invention is excellent in transmission characteristics. For example, with respect to a double-sided copper-clad laminate obtained by laminating copper foil on both sides of the laminate, a predetermined amount is applied to one copper foil using a lithography method. A conductive pattern including a pair of transmission lines (a pair of microstrip lines and a differential line) is formed by covering the dry film with the pattern, exposing only a desired etching portion by exposure or the like, and then etching. Create a test board with. Then, a differential signal is input to the input ends of a pair of transmission lines formed on the test board, and the signal waveforms at the output ends are compared.

The metal-clad laminate of the present invention has a small relative dielectric constant. The relative dielectric constant can be calculated, for example, by measuring the dielectric constant (ε) by a capacitance method using an impedance analyzer after removing the copper foil of the double-sided copper-clad laminate by etching.
The relative dielectric constant of the metal-clad laminate of the present invention is usually 3.5 or less.

  The metal-clad laminate of the present invention having the above characteristics can be suitably used as a circuit board material for electric / electronic devices. More specifically, it is suitable for single-sided, double-sided or multilayered substrate materials, and core materials for package substrates.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.
In addition, evaluation or measurement of insulation strength, crack (oxidation erosion degree), transmission characteristics, and relative dielectric constant was performed by the method shown below.

(Insulation strength)
A copper-clad laminate (metal-clad laminate) from which copper foil has been removed by etching is used as a test piece, which is put into an oven at 200 ° C. and left for 400 hours. From Va, the retention (Va / Vb) was measured.
The dielectric breakdown voltage is a voltage when dielectric breakdown is reached by applying 50 Hz alternating current to the sample using a φ24 mm electrode in air at a temperature of 23 ° C. and increasing the voltage at 0.5 kV / sec. (Based on ASTM D149).
Usually, if the retention is 0.7 or more, it can be said that the insulation strength is high.

(Crack (oxidation erosion degree))
After removing the copper foil of the copper clad laminate (metal clad laminate) by etching into an oven at 200 ° C. and placing it for 400 hours, the oxidation depth from both surfaces (by cross-sectional observation using an optical microscope) The thickness of the discolored part) was measured, and the oxidation erosion degree was calculated from the following formula.

(Transmission characteristics)
Using a lithography method, one copper foil of a double-sided copper-clad laminate is coated with a dry film in a predetermined pattern, and only the desired etching portion is exposed by an exposure and development process, followed by etching with an etching solution. Thus, a test substrate having a conductor pattern including a pair of transmission lines (a pair of microstrip lines and a differential line) having a wiring width of 100 μm and a wiring interval of 100 μm was obtained.
A 10 GHz differential signal is input to the input ends of a pair of transmission lines (a pair of microstrip lines and differential lines) formed on the test substrate, and the signal waveforms at the output end (transmission length 20 cm) are compared, and the peak position The delay characteristics were evaluated based on the following criteria.
○: Peak position is matched ×: Peak position is not matched

(Relative permittivity)
A copper-clad laminate (laminated body) from which copper foil has been removed by etching is measured using an impedance analyzer (model number E4991A, manufactured by Agilent Technologies) at a frequency of 1 GHz and a dielectric constant (ε) at 20 ° C. The relative dielectric constant (εr) was calculated.

(Production Example 1) Preparation of polymerizable composition 1 Benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride 0.6 part, triphenylphosphine 0.12 part, Was dissolved in 18.1 parts of indene to prepare a catalyst solution.
Apart from this, as cycloolefin monomer, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene (ETD) 40 parts, dicyclopentadiene 60 parts, and 2,6-bis (1,1-dimethylethyl) -4-methylphenol 0.28 as an antioxidant Into a glass container, 100 parts of silica (silane coupling agent-treated product, average particle size 0.5 μm) as an inorganic filler, 31 parts of trimethylolpropane trimethacrylate as a crosslinking aid, and Then, 60 parts of aluminum dimethylphosphinate was added as a flame retardant and mixed uniformly.
Next, 2 parts of styrene as a chain transfer agent and 2 parts of di-t-butyl peroxide as a crosslinking agent were added thereto to obtain a monomer liquid.
The entire amount of the metathesis catalyst solution was added to the obtained monomer solution and stirred to obtain a polymerizable composition 1.

(Manufacture example 2) Manufacture of layer (prepreg) 1 of a crosslinkable resin molded object The polymeric composition 1 obtained by manufacture example 1 was used for the fibrous support 1 (IPC product number # 1027, fiber-opening treatment) with a thickness of 20 micrometers. , Manufactured by Nittobo Co., Ltd.), and a polyethylene terephthalate film (PET film) having a thickness of 50 μm was bonded to both surfaces as a support film. This was heated at 120 ° C. for 3.5 minutes for a polymerization reaction, and then the support film was peeled off to obtain a crosslinkable resin molded product 1 (PP1) having a thickness of 50 μm. The ratio (TpA / TA) of the total thickness TpA of the resin layer constituting PP1 and the thickness TA of PP1 of the obtained PP1 is 0.6.

Production Example 3 Production of Crosslinkable Resin Molded Body Layer (Prepreg) 2 Polymerizable composition 1 obtained in Production Example 1 was used to form a fibrous support 2 having a thickness of 43 μm (IPC product number # 1078, with fiber opening treatment) , Manufactured by Nittobo Co., Ltd.), and a PET film having a thickness of 50 μm was bonded to both sides as a support film. This was heated at 120 ° C. for 3.5 minutes to conduct a polymerization reaction, and then the support film was peeled off to obtain a crosslinkable resin molded product 2 (PP2) having a thickness of 100 μm. The value of TpB / TB of PP2 obtained is 0.57.

(Manufacture example 4) Manufacture of layer (prepreg) 3 of a crosslinkable resin molded object In manufacture example 3, except changing fibrous support 2 into fibrous support 1, it is the same as manufacture example 3, and thickness is 100 micrometers. The crosslinkable resin molding 3 (PP3) was obtained. The value of TpB / TB of the obtained PP3 is 0.80.

(Manufacture example 5) Manufacture of the layer 4 of a crosslinkable resin molding The polymeric composition 1 is applied to one side of a 50-micrometer-thick PET film (support film), and another 50-micrometer-thick PET film is applied to the coating surface. Pasted together. This was heated at 120 ° C. for 3.5 minutes for a polymerization reaction, and then the support film was peeled off to obtain a crosslinkable resin molded product 4 (PP4) having a thickness of 100 μm. The ratio (TpB / TB) of the total thickness TpB of the resin layer constituting PP4 and the thickness TB of PP4 of the obtained PP4 is 1.00.

(Manufacture example 6) Manufacture of the layer (prepreg) 5 of a crosslinkable resin molded object In manufacture example 3, the fibrous support body 2 is made into the fibrous support body 3 (IPC product number # 2013, opening process existence, Nitto, 70 micrometers in thickness. A cross-linkable resin molded product 5 (PP5) having a thickness of 100 μm was obtained in the same manner as in Production Example 3 except that the product was changed to “Spun”. The value of TpB / TB of the obtained PP5 is 0.30.
The Tp / T values of PP1 to PP5 obtained in Production Examples 2 to 6 are summarized in Table 1 below.

Example 1
PP1 and PP2 obtained in Production Examples 2 and 3 are stacked in the order of PP1 / PP1 / PP2 / PP2 / PP1 / PP1, and this is sandwiched between 18 μm-thick copper foils and heated at 220 ° C. for 2 hours at 3 MPa. The copper-clad laminate 1 was obtained by pressing. The obtained copper-clad laminate 1 was evaluated for insulation strength, cracks, transmission characteristics, and dielectric constant. The results are shown in Table 2 below.

(Example 2)
In Example 1, a copper clad laminate 2 was obtained in the same manner as in Example 1 except that the laminated structure of the prepreg was changed to PP1 / PP1 / PP3 / PP3 / PP1 / PP1. The obtained copper-clad laminate 2 was evaluated for insulation strength, cracks, transmission characteristics, and dielectric constant. The results are shown in Table 2 below.

(Example 3)
In Example 1, the copper clad laminated body 3 was obtained like Example 1 except having changed the laminated structure of the prepreg into PP1 / PP1 / PP4 / PP4 / PP1 / PP1. The obtained copper-clad laminate 3 was evaluated for insulation strength, cracks, transmission characteristics, and dielectric constant. The results are shown in Table 2 below.

(Comparative Example 1)
In Example 1, a copper clad laminate 1r was obtained in the same manner as in Example 1 except that the laminated structure of the prepreg was changed to PP1 / PP1 / PP4 / PP4 / PP1 / PP1. The obtained copper-clad laminate 1r was evaluated for insulation strength, cracks, transmission characteristics, and dielectric constant. The results are shown in Table 2 below.

(Comparative Example 2)
In Example 1, a copper clad laminate 2r was obtained in the same manner as in Example 1 except that the laminated structure of the prepreg was changed to PP2 / PP1 / PP1 / PP1 / PP1 / PP2. The obtained copper-clad laminate 2r was evaluated for insulation strength, cracks, transmission characteristics, and dielectric constant. The results are shown in Table 2 below.

(Comparative Example 3)
Four prepregs obtained in Production Example 3 were stacked, sandwiched between 18 μm thick copper foils, and heated and pressed at 3 MPa for 2 hours at 220 ° C. to obtain a copper-clad laminate 3r. The obtained copper-clad laminate 3r was evaluated for insulation strength, cracks, transmission characteristics, and dielectric constant. The results are shown in Table 2 below.

From Table 2, the copper-clad laminates 1 to 3 obtained in the examples are compared with the copper-clad laminates 1r to 3r of the comparative example even when placed at a high temperature of 200 ° C. for 400 hours. It can be seen that the degree of oxidative erosion is small, the insulation strength is excellent, the dielectric constant is small, and the transmission characteristics are also excellent.
On the other hand, the copper-clad laminate 1r of Comparative Example 1 using a crosslinkable resin molded product having a TpB / TB of 0.4 or less at the center is inferior in transmission characteristics. The copper clad laminates 2r and 3r of Comparative Examples 2 and 3 in which the thickness of the crosslinkable resin molded body of the outermost layer is larger than or the same as the thickness of the crosslinkable resin molded body of the central portion are inferior in insulation strength and cracks. The occurrence is large.

a1, a2 ... resin layer s ... fibrous support TpA ... thickness TA of resin layer (a) ... thickness (A1) of crosslinkable resin molded product (A), (A2) ... Crosslinkable resin molded body (A) layer (B) ... crosslinkable resin molded body (B) layer L ... laminate

Claims (7)

A layer made of a crosslinkable resin molded body (A) having a resin layer on both sides of a fibrous support, a layer made of a crosslinkable resin molded body (B) having a resin layer containing an inorganic filler, and the crosslinkable resin A laminated body having a thickness of 2 mm or less, in which at least three layers are laminated in the order of the layer comprising the molded body (A),
The layer composed of the crosslinkable resin molded body (A) is disposed on both outermost layers of the laminate,
The thickness (TA) of the layer composed of the crosslinkable resin molded body (A) is smaller than the thickness (TB) of the layer composed of the crosslinkable resin molded body (B), and
The ratio (TpB / TB) of the total thickness (TpB) of the resin layer constituting the crosslinkable resin molded body (B) and the thickness (TB) of the layer made of the crosslinkable resin molded body (B) is 0.4 or more. A laminate having a thickness of 1.0 or less.   The laminate according to claim 1, wherein the resin layers of the crosslinkable resin molded body (A) and the crosslinkable resin molded body (B) are layers containing a cycloolefin resin.   The ratio (TpA / TA) of the total thickness (TpA) of the resin layers constituting the crosslinkable resin molded body (A) and the thickness (TA) of the layer made of the crosslinkable resin molded body (A) is 0.00. The laminate according to claim 1 or 2, which is 3 or more and less than 1.0.   The laminated body in any one of Claims 1-3 whose thickness of the said fibrous support body is 10-50 micrometers.   The laminate according to any one of claims 1 to 4, wherein a relative dielectric constant calculated from a dielectric constant measured at a temperature of 20 ° C and a frequency of 1 GHz using an impedance analyzer is 3.5 or less.   The crosslinkable resin molded article (A) is obtained by polymerizing the polymerizable composition after coating or impregnating a fibrous support with a polymerizable composition containing a metathesis polymerizable monomer. The laminated body in any one of Claims 1-5.   A metal-clad laminate in which a metal foil is laminated on at least one surface of the laminate according to claim 1.

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